Asphalt product and preparation thereof



ASPHALT PRQDUCT AND PREPARATION THEREOF John C. Illman, El Cerrito, Calih, assignor to Shell Development Company, ew York, N. 1., a corporation of Delaware No Drawing. Application January 17, 1955, Serial No. 432,385

Claims. (ill. 196-42) This invention relates to an asphalt product and a method for its preparation. More particularly, it is concerned with the preparation of an asphalt product having characteristics of an air blown asphalt.

Asphalts are roughly divided into several categories, the most extensive of which are paving and roofing grades of asphalts. The latter are dependent upon the softening point-penetration relationship for their utility and require a relatively low response to thermal influences. Normally, roofing grade asphalts are prepared by air blowing asphaltic residues or otherwise oxidizing them, sometimes in the presence of certain catalysts, such as ferric chloride.

In order to obtain proper dispersion of these air blown asphalts so as to reach a desired consistency at application temperatures and for later optimum properties, it has been necessary to blow in the presence of petroleum raffinates obtained by the extraction of aromatic hydrocarbons from heavy petroleum distillates. The rafiinate's are high viscosity index parai'linic distillates containing substantially no polyaromatic compounds and it has been found that they are most suitable as cutter stocks for asphalts to obtain the properties most desired in coating grade asphalts.

ecause of the widespread demand for such stocks for other uses, the heavier petroleum rafiinates are relatively expensive materials as compared with the unextractcd distillates. These distillates usually are heavier than kerosene but have not been subjected to extraction of aromatics and, therefore, contain from about to about 60% by weight of aromatic hydrocarbons. While these bulk distillates have heretofore been used for blending with straight run asphalts to be used as paving grade products, they have not been satisfactory for use with air blown asphalts due to the poor penetration-softening point relationship which results.

At the present time, due to the development of a number of different petroleum refining processes, hard asphaltic residues are being obtained as compared with the relatively softer materials normally prepared heretofore. While these may be blended with softer asphalts to obtain products having suitable properties for paving purposes and the like, it would be desirable to utilize their high softening points and other properties if an economical application can be found.

It is an object of the present invention to utilize high softening point asphalts which are normally brittle, hard materials at about room temperatures. It is another object of the present invention to provide improved asphaltic compositions. It is a further object of this invention to provide blown type asphalt compositions without resorting to air blowing operations. Other objects will become apparent during the following discussion.

Now, in accordance with the present invention, it has been found that asphalts having a minimum chemically bound nitrogen content of about 1% and normally solid and brittle at ordinary room temperatures may be converted to products having substantially higher penetration rates Patent EQQ indices by treatment of the asphalt in particulate form with a hydrogen halide at relatively low temperatures. More particularly, pulverized high softening point asphalts may be treated with gaseous or aqueous hydrogen halides to produce a product which, when dispersed in a bulk distillate, provides a composition having blown asphalt properties.

The softening point and penetration characteristics are useful guides toward the selection of bitumens which are suitable In general, asphalts passing the crushing-onpaper test will have a 0-5 penetration (ASTM D5-25 77 F, -gram load, 5 seconds). With the harder grades of asphalt, it is desirable to modify the AST M D5-25 test by employing a temperature of F. and a ZOO-gram load, instead of the conventional 77 F. and IOO-gram load. Under such conditions the operable asphalts generally show a 5-35 penetration. in addition to such penetration characteristics, these asphalts will generally be found to have a 280-340 F. softening point, and it is preferred to employ those with a 285-320 F. softening point. Corresponding coal tar pitches passing said crushing-on-paper test generally have a 265-340 F. softening point (ASTM D36-26) and an ASTM -25 (77 F., l00-gram load, 5 seconds) penetration of 0-5 and, correspondingly, an ASTM D5-25 115 F, ZOO-gram, 5 seconds, penetration of 0-40.

An example of a suitable asphalt is that produced by taking a 50/60 penetration standard paving grade asphalt, which may contain as much as 60% of oil, and steam distilling this asphalt under a high vacuum, e. g., about a 28-inch vacuum (2-inch absolute pressure), to remove nearly all of the oil. A satisfactory asphalt of the type employed in our invention can be made in this manner by steam refining the asphalt in a shell still under high vacuum. In a typical case, a 30 to 40% yield of brittle asphalt is produced, based on the paving grade asphalt charged to the still. Different asphalts will require refinement to different softening points to produce asphalts of the desired brittleness; thus, a typical California asphalt steam refined under high vacuum to a softening point of 300 F. was satisfactory. Other asphalts may require refinement to a higher softening point, while some asphalts are suitable although refined to a much lower softening point.

Suitable asphalls of the type employed according to this invention can also be prepared by the solvent refining of asphaltic petroleum oil, according to processes widely known and used in petroleum refining. Such solvent refining which involves the extraction of asphalt is advantageous in connection with the practice of this invention for various reasons, included among which is the easy control of the asphaltic oil content of the asphalt. Solvent extraction of asphalt has been widely described in petroleum refining literature. See, for instance Abraham, Asphalts and Allied Substances, D. Von Nostrand Co., Inc., New York, 5th ed., pp. 135-139; Liquid propaneuse in dewaxing, deasphalting and refining heavy oils, R. E. Wilson, P. C. Keither, Jr., and R. E. l-laylett, J. Ind. Eng. Chem. 28, 1065 (1936).

Among the solvents employed in the solvent extraction of asphalt are liquid sulfur dioxide; liquid hydrocarbons, such as liquefied ethane, pentane, propane, butane; benzol; toluol; furfural, etc, and mixtures of such solvents as, for example, propane with cresol. In general, liquid propane has been found to be the most satisfactory solvent in connection with the solvent extraction of asphalt. In a typical pro-pane process, propane is liquefied by compression and passed to the bottom of a deasphalting tower where it flows upward countercurrently to descending reduced asphaltic crude oil. The liquid propane dissolves the non-asphaltic portion of the oil and preferentially precipitates the asphalt. The deasphalted oil is Withdrawn overhead and the asphalt is removed from the bottom of the tower. At propane temperatures in the range of 100450 F., asphalt is only slightly soluble in the propane, whereas the remaining components of the reduced asphaltic crude oil are largely soluble therein at such temperatures. To extract the asphalt from the reduced crude, the latter is usually mixed with 4 to 6 times its volume of liquid propane at 120-150 F. Pressures employed are those required to maintain the solvent in a liquid state, and range from about 100-350 pounds per square inch absolute.

Oil-dissolving properties of liquid propane for the oil components of the reduced crude decrease as the temperature rises above 100 R, and it is accordingly possible to regulate the physical properties of the precipitated asphalt by varying the severity of the oil-dissolving step.

The hydrogen halide to be utilized in the present process may be either in a gaseous form or in an aqueous medium. Preferably, a gas is employed and still more preferably is dispersed in a relatively inert gaseous diluent, such as nitrogen or other similar inert gas. While hydrogen chloride is the preferred material, other hydrogen halides, such as hydrogen bromide and hydrogen iodide or mixtures thereof, may be employed. It is preferred that the agent be utilized in the gaseous or vaporized condition but may instead be contacted with the particulate asphalt in aqueous form, such as concentrated aqueous hydrochloric acid. In order to be efiective within the relatively short operating period desired, the hydrogen halide should be present, when dispersed in a gas, in a concentration between about 0.5% and about 100%, preferably between 1 and 10%; and when in an aqueous (or other liquid) medium, the hydrogen halide should comprise between about 10 and about 50% by weight thereof. Between about 1% and about 25% by weight, based on the asphalt should be used, although substantially little, if any, of this is consumed by reaction with the asphaltic particles; hence, the halide may be recycled. Hydrogen halide donors, such as the phosphorus halides, may be used in place of or in addition to the hydrogen halides per se.

The treating temperatures necessary to impart improved softening point and penetration characteristics to the particulate asphalt are surprisingly low and may be in the order of from about C. to about 50 C. and preferably are between about C. and about 40 C. Ordinary room temperatures of about C. result in rapid attainment of the desired improvement in physical properties of the asphalt.

The time of treatment at the temperatures just specified is in the order of between about seconds and about two hours. Ordinarily, no longer than about 15 minutes of treatment is necessary and times between about one and about ten minutes when utilizing gaseous HCl in contact with the particulate asphalts at a temperature of about 20-30 C. have been found adequate to produce substantially improved softening points and penetrations.

The products obtained by this process do not appear to have changed with respect to the asphaltene-maltene ratio as determined by isopentane solubility. However, the asphaltene content of the treated material is less soluble (or less strongly peptized) by a lubricating oil distillate blending agent and thereby results in the blended product having blown asphalt properties.

In further accordance with the present invention, the process has been found to be limited to those brittle asphalts containing relatively high nitrogen contents (e. g., above about 1%). When the nitrogen content of the asphalt is below about 1% by weight thereof, the alteration in physical properties under the conditions of the invention do not occur to any appreciable extent. Consequently, the present invention is limited in its most preferred aspect to the utilization of brittle asphalts having a nitrogen content greater than about 1% by weight and usually in the order of 1.5-4% by weight thereof. When asphalts having the relatively high nitrogen contents specified are treated in accordance with the process of the present invention, the reaction rapidly causes an increase of at least about 10 F. in softening point as well as improving the penetration characteristics. This distinguishes the present process from the case wherein asphalt is dissolved in its naturally occurring medium, namely, in a. crude oil, such that the average nitrogen content is below the above-stated minimum desired limit. The treatment of such a crude oil, consequently, would not result in the alteration of the asphaltic properties as is attained by the present process. Nitrogen deficient hard particulate asphalts may be treated in accordance with this invention by supplementing their natural nitrogen content with a nitrogen-rich asphalt, nitrogen-containing resins obtained from natural sources such as tar sands, shale oil, asphalts, etc., or with synthetic nitrogenous resins.

In carrying out the process of the present invention, fluidized bed techniques are preferred. Thus, the finely divided brittle asphalt is preferably passed countcrcurrent to a stream of the hydrogen halide, which is preferably in a gaseous phase. Under these conditions, the product may be passed from the top to the bottom of the tower and if necessary recycled for further treatment. Alternatively, of course, the equipment may be arranged in such a way that portions of. the treated product may be withdrawn at any point in the tower so as to obtain a series of products from the same tower having a varying degree of alteration of the softening point and penetration relationships upon dispersal in bulk distillate subsequent to the hydrogen halide treatment.

The proportion of hydrogen halide consumed by reaction or operating losses in this process is normally no more than about 5% by weight of the particulate asphalt, and may be as low as about 0.25%. Ordinarily, between about 1 and about 2.5% by weight of acid is utilized in the conversion. This, of course, will depend in part upon the degree of alteration desired and upon other factors, such as the nitrogen content of the brittle asphalt and the treating conditions employed. It is a highly desirable condition to employ the minimum amount possible for the desired change. In this respect, the utilization of hydrogen chloride in an amount of about l-10 pounds per hundred pounds of pitch is preferred since this entails a current cost of only about l0-100 cents per barrel of the blended asphalt later obtained by combination of the treated pitch and the blending stocks to be described hereinafter.

The degree of comminution of the brittle pitch is not a critical factor in the successful operation of the present process. However, for obtaining a product each particle of which is uniformly affected throughout the entire body of the particle with the hydrogen halide treatment, it is desirable that the particles be between about 0.5 and about 200 microns in average diameter. The size of the particles, if within this range, not only promotes uniformity of the resulting product, but also promotes favorable movement of the body of the particles by fluid bed techniques.

In accordance with a preferred version of the present process, it has been found that the hydrogen halide treatment may be reduced to a minimum by preparing the particles in such a way that they each possess a minimum surface area, namely, that approximating a sphere. Since the characteristic fracture of brittle asphalts results in highly irregular faces, such as would be obtained by the shattering of glass, for example, the particles produced by ordinary pulverizing techniques, such as in a ball mill or the like, have an undesirably high surface area. By treating the particles in such a way as to form spherical shapes, the treating time may be reduced by a factor of at least six fold to reach the same alteration in physical properties.

Spherical particles may be prepared by several alternative processes, for example, when the pitch is first 0btained in the form of a hot residue from a vacuum flash ing operation or the like, it is in satisfactory condition for atomizing into a suitable relatively inert atmosphere (or into a hydrogen halide atmosphere) to produce a powdered product having a desired spherical shape. Alternatively, the liquid product, when solidified, may be crushed and comminuted by a ball mill technique or equivalent process after which the particles may be treated to obtain the desired roundness. This may be effected by suspending the pitch particles in water preferably containing a water-soluble surfactant and warming to such an extent that the particles assume the desired round shape, after which the water is drained and the product dried, if required. Drying is unnecessary at this stage if the product is subsequently to be treated with an aqueous hydrogen halide.

The presence of the water-soluble surfactant appears to be highly desirable for the purpose of maintaining the particles discrete during this warming treatment. In the absence of the surfactant, it has been found that the particles when warmed tend to agglomerate into still larger bodies and, thus, defeat the purpose of the operation. The surfactants which are suitable for the purpose include soaps (preferably alkali metal soaps) of fatty acids, hydroxy fatty acids, petroleum sulfonates and lignosulfonates, especially those having 12-30 carbon atoms per molecule. Sodium ligno-sulfonate, sodium petroleum sulfonate, potassium oleate, sodium 12-hydroxy stearate and other well known equivalent materials may be utilized in an amount of about 0.1 to about 1%, based on the water employed, for the dispersion of the pitch par ticles.

The proportion of Water employed in this operation is not critical but should be sufiicient to disperse the particles present in a reasonably fluid form for easy handling. Subsequent to the warming operation, the water is drained and the product subjected to the action of the hydrogen halide. The time of warming, also, is not critical and the temperature likewise. The temperature and time will vary with the softening point of the asphalt being treated. Ordinarily, it will be suificient to operate at temperatures below the boiling point of water and at atmospheric pressure. It usually is unnecessary to heat the entire body of each individual particle, but merely just soften the outer surfaces of the particles sufiicient for them to assume the desired spherical shape.

Subsequent to the treatment of the particulate residues with the hydrogen halide, it may be desirable to wash the product with water or other hydrogen halide solvent (which is a non-solvent for the particles) for the purpose of removing any excess halide from the surfaces. For purposes where the presence of hydrogen halide impurities is of no consequence or where the residual traces of halide can evaporate before incorporation in the bulk distillate, this washing operation may be omitted. When used, it is preferably carried out at ordinary room temperatures using a minimum amount of water in multiple number of short washes interspersed by draining after which the particles may be utilized as such or may be combined with the blending stocks.

The treated asphalt particles may be combined with a number of different petroleum distillates or blended with other asphalts in order to obtain products useful either for coating or for paving purposes. The distillates especially useful in this connection are those having boiling points above the kerosene range and preferably in the lubricating oil range. As already pointed out, coating grades of asphalt normally require the use of raffinates containing substantially no condensed aromatic or resinous hydrocarbons. In accordance with the present invention, however, it has been found that coating grade asphalt compositions can be prepared from the pitches treated as just described by blending therewith a whole (bulk distillate) petroleum fraction of suitable viscosity containing any amount of aromatic hydrocarbons and normally between 15 and about 60% by weight thereof. The incorporation of between about 30% and about 70% by weight petroleum distillate, based on the entire blend of the treated asphalt and bulk distillate, results in the formation of asphaltic compositions having highly desirable coating grade properties. This is brought out more particularly in the examples which follow.

Suitable lubricating oil or pale oil fractions which may be employed include bulk distillates having a viscosity of from about SUS at 100 F. to about 300 SUS at 210 F. and may contain aromatics in the order of 15- 60% and flash points above about 300 F. More desirably the aromatics are confined to the range 15-30%, especially where coating grade asphalt compositions are desired.

In this connection, reference is made to co-pending application Serial No. 391,126, filed November 9, 1953, describing plastisols wherein asphalt particles are dispersed in suitable bulk distillates such as those just described. These compositions may be applied in fluid (plastisol) state and thereafter heated sufficiently to coalesce the particles of asphalt and the bulk distillate to from a whole asphalt coating or paving composition. The application just referred to shows that it is essential that the particles of asphalt possess a surface which is resistant to progressive solution in the suspending liquid.

It has been found that treatment of the particles of asphalt with a hydrogen halide does not provide the surfaces with the desired amount of resistance to solution upon storage. Consequently, it is necessary to further treat the hydrogen halide treated particles for this purpose if plastisol compositions are to be made. This is most conveniently carried out by briefly washing the particles with a lower molecular weight alkane containing less than about 10 carbon atoms per molecule. Preferably, the alkane is one having between about 3 and about 7 carbon atoms per molecule, such as propane, butane, heptane and hexane. Heptane is preferred.

Under the most desirable conditions, the particles, which in the present instance have been treated with the hydrogen halide, are subjected to a brief washing with the alkane at room temperature or below and at atmospheric pressure or superatmospheric pressure. This action removes maltenes from the surface of the particles, thus leaving the surfaces relatively rich in asphaltenes and, consequently, promoting resistance to solution in the suspending liquids, such as bulk distillates. Other means may be taken for providing the particles with a resistance to ready solution in a suspending liquid, such as providing the surfaces of the particles with organic plastic continuous coatings, including cellulose ethers (ethyl cellulose), cellulose esters (cellulose acetate), and other well-known plastic materials which would provide the particles with greater resistance to solution in the suspending oils.

The examples which follow illustrate the process of the present invention and the products obtained thereby:

Example 1 Hard asphalts were prepared by molecular still distillation of crude oils obtained from Western Canada, Venezuela and West Texas. The asphalts so prepared had zero penetration at 77 F. They had nitrogen contents of 0.9, 0.8 and 0.6%, respectively. The solid asphalts were ground to particle size less than about 70 microns, after which they were treated with concentrated aqueous hydrochloric acid at room temperature for about 15 minutes, then washed and dried. The penetration and softening points of these materials had not changed appreciably from those of the untreated asphalts.

The same treatment was performed on zero penetration asphalt obtained from Los Angeles Basin crude. This asphalt had a nitrogen content of 2.1. Treatment of the pulverized hard asphalt with concentrated aqueous '7 hydrogen chloride at room temperature for 15 minutes resulted in the following changes in physical properties:

Untreated Treated Softening Point, F 304 348 Penetration at 77 F., dmrn 0 Example 2 Cracked asphalt particles having an original penetration of zero at 77 F. were packed loosely in a column through which dry hydrogen chloride gas dispersed in nitrogen was passed for a period of about 30 minutes at room temperature. The nitrogen contained about 2% dry hydrogen chloride and the total amount of hydrogen chloride used, based on the weight of the asphalt particles, was about 15%. However, no noticeable increase in the weight of the particles resulted from this treatment, any losses of 1101 which occurred being due to operations rather than reaction. The properties given below were obtained on asphalt samples dispersed in an equal weight of a bulk distillate having a viscosity of about 60 SUS at 210 F.

Property Untreated Treated Softening Potnt.. 120 17G Penetration 100 F0 Penetration Index +0. 4 +4. 4

Example 3 Example 4 When pitch particles obtained as a hard residue from a propane deasphalting procedure are ground to a particle size of about 10-100 microns diameter and subjected to the action of gaseous hydrogen chloride dispersed in CO2 for a period of about 15 minutes at a temperature of about 25 C., and dispersed in a bulk distillate having a viscosity of about 200 SUS at 210 F., the composition has a substantially increased penetration index.

Example 5 Hard asphalts which have been treated with HCl give blended coating grade asphalts which possess improved durability. Coating grade asphalts of 14-20 penetration and 202-2l7 F. softening point, blended from 60 parts of hard untreated asphalt and 40 parts of the lube oil raffinate resulting from the extraction and subsequent sulfonation of a 60 SUS at 210 F. lube distillate failed after 1 cycle in a Twin Arc Weather-Ometer (ASTM Cycle A). On the other hand asphalts of 14-18 penetration and 211-221 F. softening point blended from 60 parts of the same hard asphalt after HCl treatment and 40 parts of the lube distillate, 6O SUS at 210 F., endured 3 weatherometer cycles.

The data given in Example 5 illustrate that the treatment of hard asphalts with hydrogen chloride or other hydrogen halide under the conditions of the invention results in a very substantial improvement in the weatherability of the resulting blown type asphalts as compared with ordinary coating grade asphalts prepared by conventional means.

I claim as my invention:

1. The process for modifying the properties of a petroleum residue, said residue having a nitrogen content of at least 1% by weight and being in particulate form and having a penetration of 015 decimillimeters at 77 R, which comprises contacting said residue with a gaseous atmosphere containing from about 1% to about 10% by weight of a hydrogen halide gas at a temperature between about 15 C. and about 50 C. for a period of time between about 0.5 minute and about 2 hours.

2. The process for modifying the properties of a petroleum residue, said residue containing at least 1% by weight of nitrogen chemically associated therewith, said residue being in particulate form having an average particl size between about 0.5 and about 200 microns in diameter and having a penetration of 0-15 decimillimeters at 77 R, which comprises contacting said residue with a gaseous atmosphere containing from about 0.5% to about by weight of a hydrogen halide gas at a temperature between about 20 and about 40 C. for a period of time between about 1-60 minutes.

3. The process for modifying the properties of a petroleum residue containing as a chemically bound constituent at least 1% by weight of nitrogen, said residue being in particulate form and having an average diameter between about 0.5 and about 200 microns and comprising at least about 30 by weight of maltenes, at least about 50% by weight of asphaltenes and having a penetration of O-l5 decimillimeters at 77 E, which comprises contacting said residue with a gaseous atmosphere containing from about 0.5% to about 10% by weight of hydrogen chloride gas at a temperature between about 20 C. and about 40 C. for a period of time between about 1 minute and about 1 hour.

4. The process for modifying the properties of a petroleum residue comprising at least about 1% by weight of nitrogen chemically bound in the residue molecules, said residue comprising powdered vacuum flasher pitch having a penetration less than about 15 decimillimeters at 77 F. which comprises contacting said residue with an atmosphere containing between about 1% and about 10% by weight of hydrogen chloride at a temperature between about 20 and about 40 C. for a period of time between about 1 and about 15 minutes.

5. The process for modifying the properties of a petroleum residue and preparing therefrom a coating grade asphalt product, said residue having a nitrogen content of at least 1% by weight, being in particulate form, and having a penetration of 0l5 deeimillimeters at 77 E, which comprises contacting said residue with a gaseous atmosphere containing from about 0.5% to about 100% by weight of a hydrogen halide gas at a temperature between about 15 C. and about 50 C. for a period of time between about 0.5 minute and 2 hours and thereafter dispersing the product so treated in a blending oil comprising a petroleum distillate boiling above the kerosene range and containing at least about 15% aromatic hydrocarbons.

6. The process for modifying the properties of a petroleum residue and preparing a blown type asphalt product therefrom, said residue having a nitrogen content of at least 1% by weight, a penetration of 0-15 decimillimeters at 77 F. and a particulate form having an average particle size between about 0.5 and about 200 microns in diameter which comprises contacting said residue with a gaseous atmosphere containing from about 1% to about 10% by weight of a hydrogen halide gas at a temperature between about 20 and about 40 C. for a period of time between about 1 minute and 60 minutes and thereafter dispersing the treated product in a blending oil comprising a petroleum bulk distillate boil- 10. An asphaltic product comprising an asphalt proing above the kerosene range and containing between duced by the process of claim 5. about 15 and about 60% by weight of aromatic hydrocarbons. Referenccs Cited in the file of this patent 7. A process according to claim 6 wherein the residue 5 UNITED STATES PATENTS is a propane asphalt.

8. A process according to claim 6 wherein the hydrog g g if gen halide is hydrogen chloride. 2272866 i 2 g 1942 9. A process according to claun 6 wherein the residue 2,348,832 Mauch et a1 May 16, 1944 is vacuum flasher pitch. 10 

5. THE PROCESS FOR MODIFYING THE PROPERTIES OF A PETROLEUM RESIDUE AND PREPARING THEREFROM A COATING GRADE ASPHALT PRODUCT, SAID RESIDUE HAVING A NITROGEN CONTENT OF AT LEAST 1% BY WEIGHT, BEING IN PARTICULATE FORM, AND HAVING A PENETRATION OF 0-15 DECIMILLIMETERS AT 77* F., WHICH COMPRISES CONTACTING SAID RESIDUE WITH A GASEOUS ATMOSPHERE CONTAINING FROM ABOUT 0.5% TO ABOUT 100% BY WEIGHT OF A HYDROGEN HALIDE GAS AT A TEMPERATURE BETWEEN ABOUT 15* C. AND ABOUT 50* C. FOR A PERIOD OF TIME BETWEEN ABOUT 0.5 MINUTE AND 2 HOURS AND THEREAFTER DISPERSING THE PRODUCT SO TREATED IN A BLENDING OIL COMPRISING A PETROLEUM DISTILLATE BOILING ABOVE THE KEROSENE RANGE AND CONTAINING AT LEAST ABOUT 15% AROMATIC HYDROCARBONS.
 10. AN ASPHALTIC PRODUCT COMPRISING AN ASPHALT PRODUCED BY THE PROCESS OF CLAIM
 5. 